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Process Engineering Asynchronous Learning System Neil L. Book Oliver C. Sitton Douglas K. Ludlow
Process Engineering Asynchronous Learning System Neil L. Book Oliver C. Sitton Douglas K. Ludlow
MODULE 1
Process
Engineering
Asynchronous
Learning
System
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
Department of Chemical Engineering
University of Missouri-Rolla
Rolla, MO 65409-0249
INERTING OR PURGING
This instructional module is an introduction to inerting/purging operations for process safety
applications. Inerting/purging is the use of an inert (noncombustible) gas to control the concentration of
fuel/oxygen/inert gas mixtures such that it is never in the combustible region.
Learning Objectives
1. Learn the nomenclature associated with inerting/purging operations.
2. Know the advantages and disadvantages of the common purge gases.
3. Understand the requirements for implementing the four common methods of inerting/purging: vacuum
purging, pressure purging, siphon purging, and sweep-through purging.
4. Be able to estimate the in-service oxygen concentration and the out-of-service fuel concentration for an
inerting/purging operation.
5. Be able to predict the oxygen/fuel concentration and the purge gas requirements during inerting/purging
operations.
6. Know the safety margins commonly used in inerting/purging operations.
Associated Reading
Crowl, D. A., and Louvar, J. F., Chemical Process Safety: Fundamentals with Applications, Prentice-Hall,
(1990), pp. 156-167, 194-200.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 1 of 31
Copyright 2000
CHE 258
MODULE 1
Figure 1. Triangular Composition Diagram with Typical Combustible Region for a Gaseous Fuel
The points designated A, E, and H on the diagram represent pure fuel (perhaps a mixture of
combustible substances), pure oxygen, and pure inert gas (perhaps a mixture of inert gases), respectively. The
point designated by F on the diagram represents simple air (21 mole% oxygen, 79 mole% inert, and 0 mole%
fuel).
Formula
H2
D2
CO
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Department of Chemical Engineering
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CHE 258
MODULE 1
Ammonia
NH3
15.0
79
Methane
CH4
5.1
61
Ethane
C2H6
3.0
66
Ethylene
C2H4
3.0
80
Propylene
C3H6
2.1
53
Cyclopropane
C3H6
2.5
60
Diethyl Ether
C4H10O
2.0
82
Divinyl Ether
C4H6O
1.8
85
a
The limits are insensitive to the partial pressure of water vapor above a few mmHg.
Lewis, B., and von Elbe, G., Combustion, Flames, and Explosions of Gases, 3rd Edition, Academic
Press, (1987).
Formula
Limits of Flammability
Lower
Upper
CH4
C2H6
C3H8
C4H10
C4H10
C5H12
C5H12
C5H12
C6H14
C7H16
C7H16
C8H18
C9H20
C10H22
5.3
3.0
2.2
1.9
1.8
1.5
1.4
1.4
1.2
1.2
1.1
1.0
0.8
0.8
15.0
12.5
9.5
8.5
8.4
7.8
7.6
7.5
7.5
6.7
6.7
6.0
---5.4
C2H4
C3H6
C4H8
C4H8
3.1
2.4
1.6
1.8
32.0
10.3
9.3
9.7
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CHE 258
Amylene
Acetylenes
Acetylene
Aromatics
Benzene
Toluene
o-Xylene
Cyclic hydrocarbons
Cyclopropane
Cyclohexane
Methylcyclohexane
Terpenes
Turpentine
Alcohols
Methyl alcohol
Ethyl alcohol
Allyl alcohol
n-Propyl alcohol
Isopropyl alcohol
n-Butyl alcohol
Amyl alcohol
Isoamyl alcohol
Aldehydes
Acetaldehyde
Cortonic aldehyde
Furfural
Paraldehyde
Ethers
Diethyl ether
Divinyl ether
Ketones
Acetone
Methylethyl ketone
Methylpropyl ketone
Methylbutyl ketone
Acids
Acetic acid
Hydrocyanic
Esters
Methyl formate
Ethyl formate
Methyl acetate
Ethyl acetate
Propyl acetate
Isopropyl acetate
Butyl acetate
Amyl acetate
Inorganic
Hydrogen
Carbon monoxide + water vapor at 18oCa
Ammonia
Cyanogen
Oxides
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
MODULE 1
C5H10
1.5
8.7
C2H2
2.5
80.0
C6H6
C7H8
C8H10
1.4
1.4
1.0
7.1
6.7
6.0
C3H6
C6H12
C7H14
2.4
1.3
1.2
10.4
8.0
----
C10H16
0.8
----
CH4O
C2H6O
C3H6O
C3H8O
C3H8O
C4H10O
C5H12O
C5H12O
7.3
4.3
2.5
2.1
2.0
1.4
1.2
1.2
36.0
19.0
18.0
13.5
12.0
11.2
-------
C2H4O
C4H6O
C5H4O2
C6H12O3
4.1
2.1
2.1
1.3
57.0
15.5
-------
C4H10O
C4H6O
1.9
1.7
48.0
27.0
C3H6O
C4H8O
C5H10O
C6H12O
3.0
1.8
1.5
1.3
13.0
10.0
8.0
8.0
C2H4O2
HCN
5.4
5.6
---40.0
C2H4O2
C3H6O2
C3H6O2
C4H8O2
C5H10O2
C5H10O2
C6H12O2
C7H14O2
5.9
2.7
3.1
2.5
2.0
1.8
1.7
1.1
22.0
16.4
16.0
9.0
8.0
8.0
7.6
----
4.0
12.5
15.0
6.0
75.0
74.0
28.0
32.0
H2
CO
NH3
C2N2
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Department of Chemical Engineering
University of Missouri-Rolla
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CHE 258
MODULE 1
Ethylene oxide
C2H4O
3.0
80.0
Propylene oxide
C3H6O
2.0
22.0
Dioxan
C4H8O2
2.0
22.0
Sulfides
Carbon disulfide
CS2
1.2
44.0
Hydrogen sulfide
H2S
4.3
45.0
Carbon oxysulfide
COS
12.0
29.0
Chlorides
Methyl chloride
CH3Cl
10.7
17.4
Ethyl chloride
C2H5Cl
3.8
14.8
Propyl chloride
C3H7Cl
2.6
11.1
Butyl chloride
C4H9Cl
1.8
10.1
Isobutyl chloride
C4H9Cl
2.0
8.8
Allyl chloride
C3H5Cl
3.3
11.1
Amyl chloride
C5H11Cl
1.6
8.6
Vinyl chloride
C2H3Cl
4.0
22.0
Ethylene dichloride
C2H4Cl2
6.2
16.0
Propylene dichloride
C3H6Cl2
3.4
14.5
Bromides
Methyl bromide
CH3Br
13.5
14.5
Ethyl bromide
C2H5Br
6.7
11.3
Allyl bromide
C3H5Br
4.4
7.3
Amines
Methyl amine
CH5N
4.9
20.7
Ethyl amine`
C2H7N
3.5
14.0
Dimenthyl amine
C2H7N
2.8
14.4
Propyl amine
C3H9N
2.0
10.4
Diethyl amine
C4H11N
1.8
10.1
Trimethyl amine
C3H9N
2.0
11.6
Triethyl amine
C6H15N
1.2
8.0
a
The limits are insensitive to the partial pressure of water vapor above a few mmHg.
Lewis, B., and von Elbe, G., Combustion, Flames, and Explosions of Gases, 3rd Edition, Academic
Press, (1987).
CHE 258
N2d
4
N2
5.0
5.1
5.6
12.1
11.9
11.0
11.4
11.7
12.1
CO2
5.9e
7.6e
5.9
14.6
14.6
13.4
14.3
14.1
14.5
MODULE 1
H2Oc
Ar
CCl2F2
CCl3F
Hydrogen
Hydrogenb
Carbon monoxide
2.9
Methane
12
Methaneb
13.7
9.8
Ethane
11.2
Propane
11.6
Propaneb
Butane
12.3
n-Pentane
11.8
Hexaneb
11.8
12.1
14.5
Ethylene
9.9
10.0
11.7
Propylene
11.5
11.5
14.1
2-Methylpropene
12
1-Butene
11
3-Methyl Butene
11.5
Cyclopropane
11.7
13.9
Butadiene
10.5
10.4
13.9
Acetylene
6.2
Benzene
11.5
11.2
13.9
Methyl Alcohol
9.9
Ethyl Alcohol
10.5
Dimethyl Ether
10.5
Diethyl Ether
10.2
Isobutyl Formate
12.5
Methyl Acetate
11
Methyl Ethyl Ketone
11
Carbon Disulfide
5
Natural Gas
12
Gasolineb
11.6
12.2
15.0
18.4
18.7
Jet Propulsion-4
11.5
a
the minimum oxygen concentration is the maximum concentration of oxygen that will be safe in any
unknown mixture of combustible with air and diluent gas
b
values extracted from graphs
c
temperature adjusted to give required vapor pressure of water
d
Mashuga, C. V., and Crowl, D. A., Process Safety Progress, 17, 176 (1998).
e
cannot explain large difference in values from table and graph
Lewis, B., and von Elbe, G., Combustion, Flames, and Explosions of Gases, 3rd Edition, Academic
Press, (1987).
CC HH OO O2 O
2
where:
C
H
O
CO2CO2 H 2O H 2O
CHE 258
MODULE 1
fuel 1
CO2 C
H 2O
H
2
O2 C
O H
2
4
The mole fraction for oxygen in a stoichiometric mixture of fuel and oxygen for oxygenated hydrocarbons is:
C O H
O2
2
4
xO2
fuel O2 1 O H
C
2
4
Example 1: Stoichiometric Composition for Ethyl Acetate
Determine the mole fraction of oxygen and fuel in a stoichiometric mixture of fuel and oxygen for ethyl
acetate (C4H8O2).
Solution:
The balanced chemical reaction for the complete combustion of ethyl acetate is:
C4 H 8O2 5 O
2
4 CO2
4 H 2O
5
83.3%
6
1
16.7%
6
xO2
x fuel
Mixtures with fuel and oxygen in stoichiometric proportion would be expected to be the most easily
combusted. Thus, the stoichiometric point is expected to lie between the lower and upper flammability limits for
the fuel in oxygen. In Figure 1, the stoichiometric point C is approximately 45.7 mole% fuel, 54.3 mole%
oxygen, and 0 mole% inert.
The line connecting the stoichiometric point (point C on Figure 1) with the pure inert point (point H) is the
stoichiometric line (line CH). It represents mixtures of the stoichiometric composition with pure inert, thus, the
ratio of oxygen to fuel is stoichiometric at all points on the line. The flammable region lies around the
stoichiometric line, however, the region becomes smaller as the concentration of inert increases (that is, going
from point C towards point H on the stoichiometric line). The MOC point is usually near the point where the
stoichiometric line exits the flammable region (but not necessarily at it).
The intersection of the stoichiometric line and the air line defines the stoichiometric composition in
simple air (point L on Figure 1). For a fuel that is flammable in air, the intersection will lie in the combustible
region. For Figure 1, the stoichiometric composition in air is approximately 15.1 mole% fuel, 17.9 mole%
oxygen, and 67 mole% inert.
INERTING/PURGING SCENARIOS
There are three common scenarios for inerting/purging operations. In one, a vessel containing air is to
be placed in service and, ultimately, to be filled with pure fuel. In the second, a vessel filled with pure fuel is to
Neil L. Book
277898610.doc
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Oliver C. Sitton
Department of Chemical Engineering
Douglas K. Ludlow
University of Missouri-Rolla
Copyright 2000
CHE 258
MODULE 1
be taken out of service. In the third, the composition of the gas in the vapor space of a vessel containing fuel is
to be maintained in the noncombustible region. These can be viewed as the startup, shutdown, and operating
stages of fuel storage in a vessel.
ISOC
(mole%)
5.7
7
13
11.7
12
12.5
12
12.2
10.5
12
12.5
11.7
11.5
10.8
7
11.8
10.8
11
11
11
12.7
11.7
11.5
OSFC
(mole%)
5
19.5
14.5
7
6.2
5.8
4.2
3.8
6
6
5.5
4.8
4
4.9
4
3.7
15
9.5
7.1
3.8
6.5
8.5
5.3
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 8 of 31
Copyright 2000
CHE 258
MODULE 1
Carbon Disulfide
6
2.5
Natural Gas
12.8
11
Gasolineb
12
3.8
Jet Propulsion-4
11.7
3.5
Mashuga, C. V., and Crowl, D. A., Process Safety Progress, 17, 176 (1998).
INERTING/PURGING MATERIALS
In principle, any noncombustible gas can be used for dilution purposes in inerting/purging operations.
However, nitrogen, steam, carbon dioxide, and argon are the most commonly used materials. Occasionally,
halogenated hydrocarbons, such as halon gas, are used for special applications.
Nitrogen
Nitrogen gas is the most widely used material for inerting/purging operations. It is inexpensive, widely
available, not hazardous, environmentally benign, and not prone to condensing at atmospheric conditions.
However, the minimum oxygen concentration for a fuel is typically lower with nitrogen as the diluent than with
steam or carbon dioxide. As a result, the ISOC and the OSFC are lower for nitrogen than for steam or carbon
dioxide.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 9 of 31
Copyright 2000
CHE 258
MODULE 1
Steam
The inerting/purging operation is referred to as steaming out when steam is the inert material. The air
(oxygen) in a vessel to be placed in service or the fuel in a vessel to be removed from service is steamed out.
Steam is relatively inexpensive, widely available, and environmentally benign. Steam is more hazardous than
nitrogen due to its energy content. Also, steam is prone to condense at atmospheric conditions and, if it does,
can leave a gas phase with a combustible composition. However, the minimum oxygen concentration for a fuel
at a specified temperature and pressure is higher with steam as the diluent gas than with nitrogen and, as a
result, the ISOC and/or OSFC will be higher.
Carbon Dioxide
Carbon dioxide is not as widely available as nitrogen or steam, however, it is relatively inexpensive,
environmentally benign, not hazardous, and not prone to condensing at atmospheric conditions. The minimum
oxygen concentration for a fuel is higher with carbon dioxide as the diluent gas than with nitrogen or steam and,
as a result, the ISOC and/or OSFC will be higher.
Argon
Argon gas is more expensive and tends to have a lower minimum oxygen concentration for a fuel than
nitrogen.
Halogenated Hydrocarbons
Halogenated hydrocarbons are expensive and no longer considered environmentally benign. However,
the minimum oxygen concentration for a fuel can be significantly higher with halogenated hydrocarbons than
with the other purge gases. This adds to their effectiveness for use in fire extinguishers and explosion
suppression systems.
INERTING/PURGING OPERATIONS
There are four common methods for adding inert gas: 1) vacuum purging, 2) pressure purging, 3)
siphon purging, and 4) sweep-through purging.
Vacuum Purging
If the vessel to be inerted is designed to withstand vacuum pressure, an inert atmosphere can be
created by repeatedly drawing a vacuum on the vessel and filling with inert gas. The three states of interest for
the vacuum purging process are:
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 10 of 31
Copyright 2000
CHE 258
MODULE 1
xi t
Pt
Tt
nt
ni t
The volume of the process vessel is constant throughout the inerting/purging process. For convenience, define:
V V
t1
t2
t3
Assume that the ideal gas law holds and that the temperature of the gas in the vessel is the same at all three
states for the inerting/purging process. For convenience, define:
T T t T t T t
1
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 11 of 31
Copyright 2000
CHE 258
MODULE 1
Pt V
nt
xi t
RT
ni t
1
nt
PL
where:
is the vacuum pressure (the low pressure) in the vacuum purging process.
The ideal gas law gives the total moles in the vessel.
PLV
RT
nt
2
Assuming that the composition of the gas is uniform throughout the vessel as the vacuum is drawn, then, the
composition of the gas in the vessel at state 2 is the same as at the initial state, thus:
xi t xi t
2
ni t
nt
ni t RT
PLV
Solving for the moles of the species to be diluted at the vacuum state:
ni t
xi t PLV
1
RT
Let:
x flow,i
t3
n flow t
Pt
be the mole fraction of the species to be diluted in the purge gas at time
t,
is the absolute pressure in the vessel after filling with purge gas.
PH P t
PH
where:
is the high pressure (after filling with purge gas) in the vacuum purging process.
The ideal gas law gives the total moles in the vessel after filling with purge gas:
nt
3
PH V
RT
n flow t n t n t
2
PH PL V
RT
This equation defines the purge gas requirements for the vacuum purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 12 of 31
Copyright 2000
CHE 258
MODULE 1
x flow,i x flow,i t
The moles of the species to be diluted that are added to the vessel in the purge gas is:
t3
n flow,i
t2
t3
x flow,i n flow t
So the mole fraction of the species to be diluted in the final state is:
xi t
3
ni t
nt
t3
ni t n flow,i t
2
nt
PL
L
P
x flow,i 1
P
PH
xi t
1
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel.
Example 2: Dilution of Atmospheric Air in a Vacuum Purge
Determine: a) the oxygen concentration and b) the volume of purge gas at STP when a vessel with a
volume of 4 m3 containing air at 25oC and atmospheric pressure is vacuum purged to 600 mmHg with a purge
gas that is 98 mole% nitrogen and 2 mole% oxygen. The purge gas returns the pressure in the vessel to one
atmosphere.
Solution
a)
PL
L
600mmHg
P
600mmHg
x flow,i 1 0.21
0.02 1
0.170
P
760mmHg
760mmHg
PH
xi t xi t
3
1
b)
t3
n flow t n t n t
3
t3
V flow
n flow t RT
2
P STP
STP
PH PL V
RT
PH PL V T STP
P STP T
0.771 m3 STP
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
Pt
xi t xi t
3
Pt
3
Multiple vacuum purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let t3 designate the end of the first vacuum purge cycle and the beginning of the second vacuum
purge cycle. Then,
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
t4 will correspond to a vacuum state and t5 will correspond to an inert-filled state that is the
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University of Missouri-Rolla
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Copyright 2000
CHE 258
MODULE 1
end of the second vacuum purge cycle. The mole fraction of the species to be diluted at the conclusion of the
second vacuum purge cycle will be:
Pt
P t P t
xi t
2
4
3
1
Pt
P t P t
5
3 5
xi t xi t
5
If the vacuum and inert-filled pressures are the same for each cycle
PL P t
j 1L J
2j
PH P t
j , j 1K J :
j 1L J
2 j 1
Subscript L designates the low pressure in the cycle (the vacuum state pressure) and subscript H designates
the high pressure in the cycle (the inert-filled state pressure). Measuring time in cycles (the initial time becomes
cycle 0):
xi
P
xi 0 L
PH
j 0K J
The number of such cycles necessary to achieve a target concentration for the species to be diluted is:
xi J
xi
J
P
ln L
PH
ln
J n flow t
2
J PH PL V
RT
0.06
0.21
5.3
600 mmHg
760 mmHg
ln
ln
Six cycles will be required to reduce the oxygen concentration below 6 mole%.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 14 of 31
Copyright 2000
CHE 258
MODULE 1
Pressure Purging
If the vessel to be inerted is designed to withstand elevated pressure, an inert atmosphere can be
created by repeatedly pressurizing the vessel by filling with inert gas, allowing the purge and residual gases to
mix, and then relieving the pressure. The three states of interest for the pressure purging process are:
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 15 of 31
Copyright 2000
CHE 258
MODULE 1
Take the system to be the gas in the process vessel and let:
xi t
Pt
Tt
nt
ni t
x flow,i
t2
be the mole fraction of the species to be diluted in the purge gas at time
t,
n flow t
Pt
is the absolute pressure in the vessel after the pressurized gas is relieved.
The volume of the process vessel is constant throughout the inerting/purging process. For convenience, define:
V V
t1
t2
t3
Assume that the ideal gas law holds and that the temperature of the gas in the vessel is the same at all three
states for the inerting/purging process. For convenience, define:
T T t T t T t
1
PL P t
PL
where:
is the initial pressure (the low pressure) in the pressure purging process.
Then, at the initial state:
nt
1
xi t
1
PLV
RT
ni t
nt
ni t
xi t PLV
RT
PH P t
PH
where:
is the pressure (the high pressure) in the pressure purging process.
The ideal gas law gives the total moles in the vessel.
nt
2
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
PH V
RT
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 16 of 31
Copyright 2000
CHE 258
MODULE 1
n flow t n t n t
2
PH PL V
RT
This equation defines the purge gas requirements for the pressure purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
x flow,i x flow,i t
The moles of the species to be diluted that are added to the vessel in the purge gas is:
n flow,i
t2
t2
t1
x flow,i n flow t
So the mole fraction of the species to be diluted in the pressurized state is:
xi t
2
ni t
nt
t2
ni t n flow ,i
t1
nt
PL
L
P
x flow,i 1
P
PH
xi t
1
Assuming that the composition of the gas is uniform throughout the vessel as the pressure is relieved,
then, the composition of the gas in the vessel at state 3 is the same as at state 2, thus:
PL
L
P
x flow,i 1
P
PH
xi t xi t xi t
3
2
1
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel. Also, the nomenclature has been devised so that the equations for the purge
gas requirements and the composition of the species to be diluted are identical for vacuum and pressure
purging.
Example 3: Dilution of Atmospheric Air in a Pressure Purge
Determine: a) the oxygen concentration and b) the volume of purge gas at STP when a vessel with a
volume of 4 m3 containing air at 25oC and atmospheric pressure is vacuum purged to 1.5 atmospheres with a
purge gas that is 98 mole% nitrogen and 2 mole% oxygen.
Solution
a)
PL
L
1.5 atm
P
1.5 atm
x flow,i 1 0.21
0.02 1
0.147
P
1.0 atm
1.0 atm
PH
xi t xi t
3
1
b)
t2
n flow t n t n t
1
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
PH PL V
RT
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 17 of 31
Copyright 2000
CHE 258
t2
V flow STP
n flow t RT
1
STP
P STP
MODULE 1
PH PL V T STP
P STP T
2.18 m3 STP
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
P t
xi t xi t
3
Pt
Multiple pressure purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let t3 designate the end of the first pressure purge cycle and the beginning of the second
pressure purge cycle. Then, t4 will correspond to a pressurized state and t5 will correspond to the relieved
state that is the end of the second pressure purge cycle. The mole fraction of the species to be diluted at the
conclusion of the second vacuum purge cycle will be:
Pt
P t P t
xi t
2
4
3
1
P
Pt
P
t5
3 t5
xi t xi t
5
If the pressurized and relieved pressures are the same for each cycle
PL P t
j 0L J
2j
PH P t
j , j 1K J :
j 0L J
2 j 1
Subscript L designates the low pressure in the cycle (the relieved state) and subscript H designates the high
pressure in the cycle (the pressurized state). Measuring time in cycles (the initial time becomes cycle 0):
xi
P
xi 0 L
PH
j 0K J
The number of such cycles necessary to achieve a target concentration for the species to be diluted is:
xi J
xi
0
J
P
ln L
PH
ln
J n flow t
2
J PH PL V
RT
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 18 of 31
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CHE 258
MODULE 1
0.06
0.21
3.1
1.0 atm
1.5 atm
ln
ln
Four cycles will be required to reduce the oxygen concentration below 6 mole%.
Siphon Purging
There are two steps in the siphon purging process: 1) displacement of gas in the vessel by filling with a
liquid and 2) displacement of the liquid in the vessel with purge gas. The states of interest for the siphon
purging process are shown in Figure 4.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
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Page 19 of 31
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CHE 258
MODULE 1
V( g ) t
V( l ) t
xi ( g ) t
be the composition of the chemical species to be diluted in the gas phase at time t,
Pt
Tt
n( g ) t
ni ( g ) t
be the moles of the chemical species to be diluted in the gas phase at time t.
x flow,i ( g ) t be the mole fraction of the species to be diluted in the purge gas at time t , and
t3
n flow ( g ) t
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
be the moles of purge gas added to the vessel as the liquid is drained.
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CHE 258
MODULE 1
The volume of the process vessel is constant throughout the inerting/purging process. For convenience, define:
V V
t1
t2
t3
Assume that the ideal gas law holds for the gas phase and that the temperature and pressure of the gas in the
vessel is the same at all three states for the inerting/purging process. For convenience, define:
T T t T t T t
1
P Pt Pt Pt
1
and:
VL V( g ) t
VL
where:
is the volume of gas when the vessel is filled with liquid (the low volume). Also, assume
that the liquid is completely drained from the vessel such that:
VH V( g ) t V
3
VH
where:
is the volume of gas when the vessel is drained of liquid (the high volume).
Then, at the initial state:
n( g ) t
1
xi ( g ) t
PVH
RT
ni ( g ) t
n( g ) t
xi ( g ) t PVH
ni ( g ) t
RT
Liquid is introduced to the vessel displacing the gas. The ideal gas law gives the total moles of gas left in the
vapor space.
n( g ) t
2
PVL
RT
Assuming that the composition of the gas is uniform throughout the vessel as the liquid is introduced, then, the
composition of the gas phase in the vessel at state 2 is the same as at the initial state, thus:
xi ( g ) t xi ( g ) t
2
ni ( g ) t
n( g ) t
ni ( g ) t RT
PVL
Solving for the moles of the species to be diluted at the vacuum state:
ni ( g ) t
2
xi ( g ) t PVL
1
RT
The ideal gas law gives the total moles in the vessel after draining the liquid:
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
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Copyright 2000
CHE 258
n( g ) t
3
MODULE 1
PVH
RT
n flow( g ) t n( g ) t n( g ) t
2
P VH VL
RT
This equation defines the purge gas requirements for the siphon purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
x flow,i ( g ) x flow,i ( g ) t
The moles of the species to be diluted that are added to the vessel in the purge gas is:
t3
t3
So the mole fraction of the species to be diluted in the gas phase after draining is:
xi ( g ) t
3
ni ( g ) t
n( g ) t
t3
ni ( g ) t n flow,i ( g ) t
2
n( g ) t
VL
V L
x flow,i ( g ) 1
V H
VH
xi ( g ) t
1
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel. The formulas for the purge gas requirements and the composition of the
species to be diluted are the same as those for vacuum and pressure purging with volume substituted for
pressure.
Example 6: Siphon Purging of Air
A 1000-gallon vessel that is filled with air at 760 mmHg and 20oC is to be inertied by siphon purging so
that benzene (C6H6) can be charged to the vessel. How many gallons of water should be to create a 5% margin
of safety in one cycle if the nitrogen purge gas contains 1 mole% oxygen?
Solution
The in-service oxygen concentration for benzene is 11.8 mole% (Table 4). A 5% margin of safety would
give a target oxygen concentration of 6.8 mole%. Assume air to be simple air and note that the ideal gas law
will be valid at these conditions:
VL
V L
VL
VL
x flow,i ( g ) 1 0.21
0.01 1
V H
1000 gal
1000 gal
VH
xi ( g ) t 0.068 xi ( g ) t
3
1
Solving for the low gas volume:
VL 290 gal
This is the gas volume when the vessel is filled with liquid. The liquid volume is:
V VL V( l ) t
V( l ) t 710 gal
2
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 22 of 31
Copyright 2000
CHE 258
MODULE 1
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
V( g )
t
xi ( g ) t xi ( g ) t
3
V( g )
t3
Multiple siphon purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let t3 designate the end of the first siphon purge cycle and the beginning of the second siphon
purge cycle. Then, t4 will correspond to a liquid-filled state and t5 will correspond to the drained state that is
the end of the second siphon purge cycle. The mole fraction of the species to be diluted in the gas phase at the
conclusion of the second siphon purge cycle will be:
V( g )
t
V( g )
V ( g ) t
t2
xi ( g )
4
t1
3 V
V( g ) t
V( g ) t
( g ) t5
3
5
xi ( g ) t xi ( g ) t
5
If the liquid-filled and drained gas volumes are the same for each cycle
VL V( g ) t
2j
VH V( g ) t
j , j 1K J :
j 1L J
j 1L J
2 j 1
Subscript L designates the low gas volume in the cycle (the liquid-filled state) and subscript H designates the
high gas volume in the cycle (the drained state). Measuring time in cycles (the initial time becomes cycle 0):
xi ( g )
V
xi ( g ) 0 L
VH
j 0K J
The number of such cycles necessary to achieve a target concentration for the species to be diluted in the gas
phase is:
xi ( g )
J
xi ( g )
0
J
V
ln L
VH
ln
J n flow ( g ) t
2
JP VH VL
RT
Again, the equations are identical to those for vacuum and pressure purging with volume substituted for
pressure.
Example 7: Number of Siphon Purge Cycles
A 1000-gallon vessel that is filled with air at 760 mmHg and 20oC is to be inerted by siphon purging so
that benzene (C6H6) can be charged to the vessel. How many purge cycles using 400 gallons of water would
create a 5% margin of safety using pure nitrogen purge gas?
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 23 of 31
Copyright 2000
CHE 258
MODULE 1
Solution
The in-service oxygen concentration for benzene is 11.8 mole% (Table 4). A 5% margin of safety would
give a target oxygen concentration of 6.8 mole%. Assume air to be simple air and note that the ideal gas law
will be valid at these conditions. Sufficient time will have to be allotted after draining to ensure that the purge
gas mixes thoroughly so the concentration in the vessel is uniform throughout.
If the filled with 400 gallons of liquid, then the gas phase volume is:
VL 600 gal
0.068
0.21
2.2
600 gal
1000 gal
ln
ln
Three cycles will be required to reduce the oxygen concentration below 6.8 mole%.
Sweep-Through Purging
The purge gas is allowed to flow continuously through the vessel in sweep-through purging. The
residual gas in the vessel can be displaced by the purge gas and/or mix with the purge gas. If the inlet and
outlet ports for the purge gas are not placed properly, the purge gas may not displace and/or mix thoroughly with
the residual gas in the vessel. Displacement effects are generally neglected in sweep-through purging.
Displacement is most effective if the flow within the vessel is laminar. Mixing, on the other hand, is most
effective when there is a lot of turbulence in the flow within the vessel. When non-ideal mixing occurs, the purge
gas is said to bypass or short-circuit (simply flow from the inlet to the outlet). Portions of the residual gas in the
vessel (particularly that in corners or indentations in the vessel) will not be displaced from the vessel nor will the
composition be diluted by the purge gas. For sweep-through purging to be effective, it is important for the purge
gas to flow throughout the entire volume of the vessel (no dead volumes or eddies). Figure 3 shows the sweepthrough purge process.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 24 of 31
Copyright 2000
CHE 258
MODULE 1
xi t
Pt
Tt
nt
ni t
V&
flow ,in
V&flow,out
n&flow,in
n&flow,out
n&flow,in ,i
be the molar flow of the species to be diluted in the purge gas into the vessel,
n&flow,out ,i
be the molar flow of the species to be diluted in the gas from the vessel,
x flow,in ,i
be the mole fraction of the species to be diluted in the purge gas into the vessel,
x flow,out ,i
be the mole fraction of the species to be diluted in the gas from the vessel,
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 25 of 31
Copyright 2000
CHE 258
Pflow,in
Pflow,out
T flow,in
T flow,out
MODULE 1
T T t T flow,in T flow,out
P P t Pflow,in Pflow,out
V V
The ideal gas law gives the total moles in the system:
nt
PV
RT
The temperature and pressure of the gas and the volume of the vessel are assumed constant, therefore:
d nt
dt
Under these assumptions, the total number of moles of gas in the vessel is constant throughout the process.
There are no chemical reactions occurring during the process, thus, the Law of Conservation of Mass can be
written in terms of moles:
d nt
dt
0 n&flow,in n&flow,out
The sign convention taken is that the molar flows, both in and out of the system, are positive. Applying the ideal
gas law to the flows:
n&flow,in
n&flow,out
PV&flow,in
RT
PV&flow,out
RT
d ni t
dt
n&flow,in ,i n&flow,out ,i
Substituting the definition of the mole fraction for the species to be diluted:
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
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Copyright 2000
CHE 258
d xi t n t
dt
flow ,in ,i
MODULE 1
In most cases, the mole fraction of the species to be diluted is negligible in the purge gas. Substituting the ideal
gas law relationships:
PV
d xi t
PV&
PV&
RT
x flow,in,i
x flow,out ,i
dt
RT
RT
The volume of the vessel, the volumetric flow of the purge gas, the temperature, and the pressure are all
assumed constant throughout the process, therefore:
d xi t
dt
Assume a very simple model for the mixing of the purge and residual gas in the vessel in which a fraction of the
purge gas mixes perfectly with the residual gas in the vessel and the remainder does not mix at all. The
nonideal mixing factor is the fraction of the purge gas that perfectly mixes. The two fractions combine to form
the gas that exits the vessel. Further assume that the fraction of perfectly mixed purge gas is constant
throughout the process. Let:
f mix
be the nonideal mixing factor.
If the nonideal mixing factor is one, then the purge and residual gases mix perfectly and if it is zero, then the
purge gas flows directly from the inlet to outlet of the vessel. In practice, the nonideal mixing factor is
somewhere between these two limits. Table 4 reports the recommended values for the nonideal mixing factor
for various ventilation conditions in which personnel may be exposed to toxic substances.
Table 4. Nonideal Mixing Factor for Various Ventilation Conditions
Recommended Values for the Nonideal Mixing Factor a
Poor
Average
Good
Excellent
Slight
1/7
1/4
1/3
1/2
Moderate
1/8
1/5
1/4
1/3
High
1/11
1/8
1/7
1/6
a
Values are reciprocals of safety factors reported.
Sax, N. Irving, Dangerous Properties of Industrial Materials, 5th Edition, Van Nostrand Reinhold, 61
(1979).
Toxicity
Process vessels, even those that are to be regularly purged, are not often designed to achieve good
mixing of the purge and residual gases. In the absence of vessel design specifically for purging, a value of 1/10
is a reasonable for design under the worst-case scenario.
For this simple mixing model:
V
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
d xi t
dt
Page 27 of 31
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CHE 258
MODULE 1
d xi t
dt
Integrating from the initial time,
f mixV&
xi t x flow,in ,i
V
t1 :
xi x flow,in,i
f V&
t
mix t t1
xi t x flow,in,i
V
ln
The total sweep gas requirements are:
t
V flow t V& t t1
1
The number of turnovers is defined as the volume of sweep gas divided by the volume of the vessel:
t
N turnover
V flow t
V& t t1
V
0.06 0.01
0.21 0.01
ln
m3
1
2
10 min
t t1
4 m3
t t1 27.7 min
Note that the total volume of sweep gas is:
m3
V& t t1 2
27.7 min 55.4 m3
min
Almost 14 turnovers are required.
Summary
Sweep-through purging is a simple process that can be accomplished at atmospheric pressure (the
vessel to be purged does not have to be designed for vacuum or pressure conditions). However, mixing
effectiveness is an important consideration in purge gas cost and time. Vessels to be sweep-through purged
should be designed to achieve good mixing.
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 28 of 31
Copyright 2000
CHE 258
MODULE 1
xi x flow,in,i
f V&
t
mix t t1
xi t x flow,in,i
V
ln
t t1
2500 bbl
1 400 cfm
31 gal 0.001
ln
bbl 1.000
2.98 hr
7.48 gal 60 min
ft 3
hr
t
N turnover
N turnover
V flow t
V& t t1
V
2.98 hr
ft 3
hr
6.91
31 gal
2500 bbl
bbl
400 cfm
b)
f mix
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
2500 bbl
31 gal 0.001
ln
bbl 1.000
0.124
7.48 gal 60 min
400 cfm
24 hr
ft 3
hr
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CHE 258
N turnover
7.48 gal
ft 3
2500 bbl
400 cfm
MODULE 1
60 min
24 hr
hr
55.6
31 gal
bbl
The non-ideal mixing factor has a value of approximately 1/8 that is indicative of poor mixing. The poor mixing
leads to long purge times and a large number of turnovers.
c)
2500 bbl
f mix
400 cfm
N turnover
31 gal 0.001
ln
bbl
1.000
0.298
7.48 gal 60 min
10 hr
ft 3
hr
7.48 gal
ft 3
2500 bbl
400 cfm
60 min
10 hr
hr
23.2
31 gal
bbl
The non-ideal mixing factor has a value of approximately 3/10 that is indicative of good mixing. The improved
mixing greatly reduces purge time and carbon dioxide consumption.
Homework Problem 258.1.2 (30 points): Vacuum Purging
The flavor of certain carbonated beverages is adversely affected by the presence of oxygen in the
gaseous atmosphere above the fluid. Storage vessels are purged of air using carbon dioxide prior to
introduction of the beverage. The storage vessels are horizontal, cylindrical tanks of 2500 barrel capacity (in
this industry, one barrel is 31 US gallons) and are rated for perfect vacuum. The carbon dioxide concentration
must be at least 99.9 mole% for beverage storage. A jet ejector is available that will draw a vacuum pressure of
10 inches of mercury. Determine the number of vacuum purge cycles and the volume of purge gas at 25 oC and
1 atmosphere necessary to purge the air from the vessel.
Solution
xi J
xi
0
J
P
ln L
PH
ln
0.001
1.000
J
17.0
29.92 inHg 10.0 inHg
ln
29.92 inHg
ln
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
Page 30 of 31
Copyright 2000
CHE 258
t3
J n flow t
2
lit atm
0.082 mole K
t3
t3
J V flow t
2
Pflow
gal
bbl
68.2 kgmole
atm kgmole
J PH PL V
17
RT
Jn flow t RT flow
MODULE 1
1000 mole
lit atm
0.082
298 K
mole K
kgmole
17 68.2 kgmole
N turnover
Neil L. Book
Oliver C. Sitton
Douglas K. Ludlow
J V flow t
V
28.3x106 lit
96.6
31 gal 3.785 lit
2500 bbl
gal
bbl
277898610.doc
Department of Chemical Engineering
University of Missouri-Rolla
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Copyright 2000